Change in Supramolecular Networks through In Situ Esterification of Porphyrins

Abstract

(5), and Co (6); Me = CH 3 ], and two nonmetalated compounds, TCPP-Et 4 (7) and TCPP-Me 4 ·H 2 O (8), were synthesized by solvothermal reactions and characterized by single-crystal X-ray diffraction. Compounds 1-3 feature an isolated structure with a planar macrocycle and an embedded metal-ion coordinating to four pyrrole nitrogen atoms. Compound 4 is characterized as a two-dimensional coordination polymer, and the zinc ion coordinates to four nitrogen atoms and two oxygen atoms. Compound 4 possesses a large void space (361 Å 3 ), which corresponds to 14 % of the unit-cell volume. Compounds 5 and 6 are characteristic of an isolated motif with a four-coordinate metal ion and a saddle-distorted nonplanar porphyrin macrocycle. Nonmetalated compounds 7 and 8 also show an

2-D metalloporphyrin coordination network of cobalt-meso-tetra(4-carboxyphenyl)porphyrin

“…The B band is observed at 410 nm. Similar observation was reported for [Co(TCPP-Me 4 )] (TCPP-Me 4 = meso-tetra(4-carboxyphenyl)porphine tetramethyl ester) [28].…”

“…Porphyrins usually exhibit an intense B band (Soret band) at about 400 nm and four less intense Q bands between 500 and 650 nm. The B band and four Q bands for free-base TCPP are located at 416, 512, 546, 590 and 645 nm [28]. Figure S2 displays the diffuse reflectance spectrum.…”

“…The main emission band of 648 nm is same as the free base of TCPP [28]. The main excitation bands are located at 416 and 479 nm.…”

β-Octafluorinated tetrakis(ethoxycarbonyl)porphyrin

“…The porphyrin core of 207 Zn-1 and Zn-2 is perfectly planar. The bond lengths from the zinc 208 ion to the pyrrole nitrogen atoms are in the range of 2.057(2)-209 2.065(2) Å in Zn-2 and 2.038(4)-2.072(4) Å in Zn-1, comparable to 210 that found in the literature [29,30]. Moreover, the hexa-coordi-211 nated Zn atom is located in the mean plane of porphyrin ring in 212 both Zn-1 and Zn-2 and is bound to two oxygen atoms from two 213 carboxyl groups at the meso position of the porphyrin molecule.…”

Self-assembly of iron TCPP (meso-tetra(4-carboxyphenyl)porphyrin) into a chiral 2D coordination polymer

“…TCPP coordination polymers with different structures have been prepared. For example, 2D porphyrin frameworks have been reported exhibiting square grid structure sustained by characteristic π-π stacking interactions and multiple hydrogen bonds [20][21][22][23]. Similarly, a 2D complex with Mn II [24] must be cited as the dimensionality is based on coordination bonds.…”